The invention relates to thermoplastic polyolefin compositions having enhanced surface durability and products thereof which include a thermoplastic polyolefin base component at least one radiation-crosslinkable component present in an amount sufficient to enhance the surface durability of the thermoplastic polyolefin component when radiation-cured and at least one photoinitiator present in an amount sufficient to initiate crosslinking of the radiation-crosslinkable component upon exposure of the thermoplastic polyolefin composition to radiation. The invention further relates to methods of providing a cured thermoplastic polyolefin composition having enhanced surface durability by preparing a mixture having a thermoplastic polyolefin base component, at least one radiation-crosslinkable component in an amount sufficient to enhance the surface durability of the polyolefin when radiation cured, and at least one photoinitiator each in an amount sufficient to facilitate crosslinking of the radiation-crosslinkable component when a surface of the thermoplastic polyolefin composition is exposed to radiation, and then exposing the thermoplastic polyolefin composition to radiation in an amount sufficient to crosslink the radiation-crosslinkable component thereby providing a thermoplastic polyolefin composition having enhanced surface durability.

This invention relates to thermoplastic, polyolefin materials (xe2x80x9cpolyolefinsxe2x80x9d) having superior mar, scratch, wear, and abrasion resistance and methods of making such polyolefins by exposure to radiation to crosslink unsaturated polyolefins therein.
Polyolefins are useful in a wide variety of applications due to their strength, environmental resistance and moldability. Many polyolefins are too easily scratched, marred, worn, abraded or otherwise damaged on their surface. These surface characteristics may be measured in a variety of ways. For example, scratch resistance may be measured by vertically penetrating a scratch needle, with a spherical tip into a polyolefin or other material surface under a constant load. The needle is then moved horizontally at a constant rate, and the width and/or depth of any formed scratch is measured (See, e.g., T. Nomura, et al., J. Applied Polymer Sci. 55:1307-1315 (1995)). Generally, it has been desired to enhance the service life of a polyolefin by improving these surface characteristics to reduce scratching, marring, wearing, abrasion, and the like.
One conventional method to enhance surface characteristics has been to use inorganic particulate material, such as various silicas. Uniform dispersion of these particulates is difficult to achieve, however, and this results in non-uniform surface properties in such products. The use of these particulates also tends to damage other desirable physical properties of the polyolefin, resulting in loss of impact strength, toughness, processability, and the like.
A more effective conventional method of providing surface enhancing characteristics to certain polyolefins is disclosed in U.S. Pat. No. 4,921,669. This patent discloses passing a web of extruded thermoplastic synthetic resin through a polishing roll stack, wherein at least one of the rolls has thereon a film of a material forming such a scratch resistant coating that is transferred from the roll to the web surface. Such conventional methods of enhancing the surface characteristics of a polyolefin require expensive, bulky equipment that also increase the processing time of polyolefin products.
Another way to enhance surface characteristics of polyolefins is described in U.S. Pat. No. 4,000,216, which discloses an extrudable, moldable, or heat formable blend of a thermoplastic polymer and a surface altering agent of at least one monoethylenically unsaturated monomer for said thermoplastic polymer, wherein the surface altering agent has cross-linked polymer particles having an average size of 1 to 30 m. The surface altering agent is preferably prepared by an endopolymerization, which is used with a compatible polyolefin to be altered.
Another conventional way to enhance surface characteristics of various articles is to apply acrylic polymers or coatings to an article and subsequently cure the polymer or coating with a radiation source, such as ultraviolet radiation (xe2x80x9cUVxe2x80x9d). The following patents describe a variety of examples of such conventional xe2x80x9capply coating and curexe2x80x9d methods and compositions.
U.S. Pat. Nos. 4,153,526 and 4,039,720 disclose safety glass made by laminating a saturated polyvinyl acetal film and a photoinitiator to a ply of glass, and irradiating the film with UV to initiate crosslinking and to provide improved solvent-abrasion resistance. U.S. Pat. No. 4,227,979 discloses radiation-curable coating compositions including one or more amide acrylate compounds that form mar-resistant protective and decorative film coatings.
U.S. Pat. No. 4,255,303 discloses a composition for coating electrical applications including ethylene polymer and at least 10 parts by weight of talc filler per 100 parts by weight of polymer, where the talc is coated with at least one metallic salt of a fatty acid having 8 to 20 carbon atoms. The ethylene polymers may be curable by irradiation with high-energy electron beams or a chemical curing agent, such as organic peroxide. U.S. Pat. No. 4,371,566 discloses actinic radiation curable coating compositions for application to many substrates having a pentaerythritol-based polyacrylate or polymethacrylate, such as pentaerythritol tetraacrylate, a vinyl chloride-vinyl acetate containing polymer, and a photoinitiator, preferably applied by spraying a solution onto the substrate.
U.S. Pat. No. 4,478,876 discloses a process of coating a solid substrate with an abrasion resistant silicone hard coating curable upon UV exposure under a non-inert atmosphere, such as air. The composition includes a UV crosslinkable polyfunctional acrylate monomer, SiO2 in the form of colloidal silica, and acryloxy functional silanes and a selected blend of ketone-type and hindered amine-type photoinitiators.
U.S. Pat. No. 4,814,207 discloses a method for applying a scratch and weather resistant film coating to a shaped article by applying to the article a thin film of a mixture of free radically polymerizable monomer having at least two polymerizable olefinic bonds, a peroxide initiator having a half life of less than two minutes at 100xc2x0 C., and an ultraviolet stabilizer, and curing the film by heating it to a temperature greater than 70xc2x0 C. U.S. Pat. No. 4,902,578 discloses a radiation-curable coating for thermoplastic substrates having a polyfunctional acrylic monomer, a mono-, di-, or trifunctional acrylic monomer, a thermoplastic or elastomeric polymer, and a photoinitiator.
U.S. Pat. No. 5,006,436 discloses a UV curable, aqueous alkaline developable solder mask composition having a thermal free radical initiator capable of generating free radicals with heat, and a polyunsaturated compound capable of being thermally crosslinked by the free radicals to provide a substantially fully cured coating. U.S. Pat. No. 5,316,791 discloses a process for improving the impact resistance of a coated plastic substrate by applying an aqueous polyurethane dispersion as a primer layer, partially curing the layer by air drying, applying a coating composition over the primer layer, and curing the coating composition to form an abrasion-resistant hard coat. U.S. Pat. No. 5,382,604 discloses a crosslinked adhesive composition having an epoxidized diolefin block polymer crosslinked by UV radiation through at least some of the epoxy functionality.
U.S. Pat. No.5,558,911 discloses a method of coating articles with powder coatings having polymers applied to the substrate to be coated, melting the polymers, and crosslinking by UV radiation.
U.S. Pat. No. 5,591,551 discloses a lithographic coating and method of coating at least a portion of a surface allow of an article with a radiation-crosslinkable polymer and exposing it to a pattern of radiation to produce an image. The polymer is disclosed to be a copolymer of an isoolefin of 4-7 carbon atoms and para-alkylstyrene.
U.S. Pat. No. 5,618,586 discloses self-crosslinkable film-forming compositions as coatings and a process for preparing multi-layered coated articles with a colored base coat and a clear top coat, wherein the composition includes a non-gelled addition polymer that is the free radical initiated reaction product of an N-alkoxymethyl (meth) acrylamide and at least one other ethylenically unsaturated monomer.
These conventional curable products generally require several steps, particularly coating or effectively laminating a prepared product with the UV-curable coating. However, it would be advantageous to provide independent polyolefin compositions that are capable of being cured without the need for additional processing steps, such as coating or laminating an article with a curable composition. It is thus desired to produce such a product, preferably one having enhanced surface durability. The present invention provides new polyolefin compositions that satisfy this need.
The present invention relates to a thermoplastic polyolefin composition having enhanced surface durability, which includes a base component of a thermoplastic polyolefin, at least one radiation-crosslinkable component present in an amount sufficient to enhance the surface durability of the thermoplastic polyolefin base component when radiation-cured, and at least one photoinitiator present in an amount sufficient to initiate crosslinking of the radiation-crosslinkable component upon exposure of the thermoplastic polyolefin composition to radiation.
In one embodiment, the polyolefin composition also includes a filler in an amount of between 0.1 to 30 weight percent. In a preferred embodiment, the filler includes calcium carbonate, clay, talc, mica, glass, zinc oxide, wollastonite, silica, titanium dioxide, or mixtures thereof.
In another embodiment, the thermoplastic polyolefin base component is thermally treated prior to or subsequent to radiation exposure. The thermal treatment may vary in intensity from 25xc2x0 C. to 150xc2x0 C. and may vary in duration from a few minutes up to a few days (e.g., from 2 minutes to 48 hours) depending on the temperature and desired extent of cure. Alternately, the base component can be subjected to a series of alternating thermal and radiation treatments which may be of varying duration lengths depending on the desired physical properties.
The compositions may contain photo-oxidative stabilizers that prevent environmental degradation of the thermoplastic polyolefin base component without interfering substantially with the photoinitiated surface crosslinking.
The thermoplastic polyolefin base component may include a blend of a crystalline or semi-crystalline poly-xcex1-olefin and an amorphous poly-xcex1-olefin. In a preferred embodiment, the thermoplastic polyolefin base component includes a blend of semi-crystalline polypropylene and amorphous ethylene/xcex1-olefin copolymer. In another embodiment, the amorphous poly-xcex1-olefin includes amorphous copolymer of ethylene and at least one diene. Generally, the thermoplastic polyolefin base component is present in an amount of about 99 to 55 weight percent of the composition. In a preferred embodiment, the thermoplastic polyolefin base component is present from about 95 to 65 weight percent of the composition.
The radiation-crosslinkable component may include an unsaturated polyolefin. In a preferred embodiment, the unsaturated polyolefin includes an ethylene, propylene and diene terpolymer; polybutadiene; polyisoprene; a styrenic polymer; an ethylene and propylene copolymer; methacrylate grafted polybutadiene or mixtures thereof. Typically, the radiation-crosslinkable component is present in an amount of about 1 to 30 weight percent of the thermoplastic polyolefin composition.
The photoinitiator may be any one of benzoin and benzoin ether derivatives; benzil ketal derivatives; xcex1,xcex1-dialkyoxyacetophenone derivatives; xcex1-aminoalkylphenone derivatives; xcex1-hydroxyalkylphenone derivatives; acylphosphine oxides; acylphosphine sulfides; phenylglyoxylate derivatives; O-acyl-2-oximino ketone derivatives; benzophenone and its derivatives; Michler""s ketone and its derivatives; thioxanthone and its derivatives; mixtures thereof; and all the polymer-bound compounds of the type mentioned above. In a preferred embodiment, the photoinitiator is benzil ketal derivatives; and acylphosphine oxides. The photoinitiator is typically present in an amount of about 0.01 to 5 weight percent of the composition. Mixtures of photoinitiators may also be used, along with accelerators that facilitate rapid crosslinking.
The invention also relates to a method of providing a cured thermoplastic polyolefin composition having enhanced surface durability by preparing a mixture of a thermoplastic polyolefin base component, at least one radiation-crosslinkable component in an amount sufficient to enhance the surface durability of the thermoplastic polyolefin component when radiation cured, and at least one photoinitiator in an amount sufficient to facilitate crosslinking of the radiation-crosslinkable component when the thermoplastic polyolefin composition is exposed to radiation, and then exposing a surface of the thermoplastic polyolefin composition to radiation in an amount sufficient to crosslink the radiation-crosslinkable component at least at the exposed surface, thereby providing a thermoplastic polyolefin composition having enhanced surface durability.
In one embodiment, the radiation is selected to be ultraviolet, electron beam, gamma, visible, microwave, infrared, or thermal radiation, or mixtures thereof. In another embodiment the radiation is imparted at a power of 0.1 J/cm2 and above and at a wavelength between about 200 to 500 nm.
In a preferred embodiment, the thermoplastic polyolefin base component is selected to be a blend of a crystalline or semicrystalline poly-xcex1-olefin and an amorphous poly-xcex1-olefin, the radiation-crosslinkable component is selected to be an unsaturated polyolefin that is present in about 0.01 to 20 weight percent of the composition, the photoinitiator is selected to be benzil ketals or phosphine oxides present in about 0.1 to 5 weight percent of the composition, and a filler is added to the mixture. The method may further include forming the thermoplastic polyolefin composition into a desired shape prior to exposing the surface of the composition to the radiation.
The invention also relates to a thermoplastic polyolefin composition having enhanced surface durability formed by the above-described method. In one embodiment, the composition has an outer surface that contains a polymerized component so that the surface scratch resistance after irradiation has a rating of 1.5 or lower on the Solvay scale (see definition below) after cure.
Polyolefin compositions having enhanced surface durability, and a process for making the same, have now been advantageously discovered. The polyolefin compositions of the present invention include a thermoplastic polyolefin base component, a radiation-crosslinkable component, and a photoinitiator, together with one or more optional fillers used to create a final product having desired characteristics. The present invention is believed to influence the mechanics of surface deformation and recovery by preferentially introducing crosslinks near the surface of a formed article made from the polyolefin composition. Thus, the polyolefin compositions exhibit superior durability and resistance to marring, scratching, wear, abrasion, and other surface damage without the need for a cumbersome coating-type process.
The terms xe2x80x9cthermoplastic polyolefin compositionxe2x80x9d or xe2x80x9cpolyolefin compositionxe2x80x9d are intended to include any composition that contains one or more crystalline or semi-crystalline olefin polymers, such as polyethylene, polypropylene or other C5-C20 olefins. The crystallinity of such olefins can range from 30 to 100%. Mixtures of these polymers are contemplated as part of the invention, as well. Other components that typically can be included in such polyolefin compositions are amorphous polymers of C3-C20 olefins, whether used alone or as co-polymers of two different olefins or as terpolymers of three different olefins. Such amorphous components are typically added to enhance the low temperature impact or paintability properties of the polyolefin composition. For example, the polymer composition of U.S. Pat. Nos. 4,945,005, 4,997,720 and 5,498,671 can be used as the polyolefin component in this invention.
The polyolefin compositions of the invention may include any thermoplastic polyolefin base component of one or more polyolefins that do not crosslink but that have compatibility with one or more unsaturated polyolefins that are capable of crosslinking under irradiation, although the polyolefin base component is preferably a polyolefin, more preferably a blend of a crystalline or semi-crystalline poly-xcex1-olefin and an amorphous poly-xcex1-olefin, and most preferably a blend of a semicrystalline propylene homopolymer or copolymer with another poly-xcex1-olefin and an amorphous copolymer or terpolymer of ethylene with another xcex1-olefin or diene. Although any diene is suitable for use in a co- or terpolymer, preferably the diene is ethylidine norbomene, dicyclopentadiene, or hexadiene. The most preferred polyolefin base component includes a semi-crystalline polypropylene blended with an ethylene/xcex1-olefin copolymer. The term xe2x80x9cpoly-xcex1-olefin(s)xe2x80x9d used in the invention means alkenes of 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, having a double bond between the first and second carbon atoms. The polyolefin component is a base component, i.e., is the predominant component in the composition, and is not capable of crosslinking under the radiation described herein. This base component is typically present in an amount of about 99 to 55 weight percent of the composition, preferably about 95 to 65 weight percent of the composition, and more preferably about 90 to 70 weight percent of the composition. The polyolefin component, or polyolefin base component, is generally the remainder of the polyolefin composition after the radiation-crosslinkable component, photoinitiator and any optional filler are combined.
The polyolefin of the polyolefin base component is considered semi-crystalline when it has a crystallinity of at least about 30%, while fully crystalline materials, having a crystallinity of from 70 to 100% as determined by X-ray diffraction, are also suitable. When polypropylene is the selected olefin, a degree of crystallinity of between 30 to 98% is acceptable to achieve sufficiently crystalline behavior, although 60 to 70% is preferred, amorphous polyolefins typically have a crystallinity of below 30%. The molecular weight average of the polyolefin is typically between 10,000 and 300,000, more typically between 50,000 and 150,000. Blends of different molecular weight polymers may be utilized, if desired.
The enhanced surface durability polyolefin composition also includes a radiation-crosslinkable component and a photoinitiator. The radiation-crosslinkable component is typically an unsaturated polyolefin. The unsaturated polyolefin may be any suitable polyolefin described herein for the polyolefin component, except that it should have at least about one percent of its covalent bonds unsaturated. It is preferred to have greater unsaturation in the radiation-crosslinkable component, which results in greater and more rapid crosslinking when exposed to radiation and ultimately enhances the surface characteristics of the polyolefin composition to a greater extent. The unsaturated polyolefin may be, for example, an ethylene, propylene and diene terpolymer; polybutadiene; polyisoprene; a styrenic polymer; a methacrylate grafted polybutadiene or a mixture thereof; or the like. Preferably, however, the radiation-crosslinkable component is an ethylene/xcex1-olefin copolymer, and more preferably an copolymer of ethylene and propylene. The radiation-crosslinkable component is present in an amount sufficient to enhance the surface durability of the polyolefin composition when radiation-cured. The radiation-crosslinkable component is preferably present in about 1 to 30 weight percent, more preferably about 5 to 20 weight percent, and most preferably about 10 to 15 weight percent, of the polyolefin composition.
The term xe2x80x9cmethacrylate grafted polybutadienexe2x80x9d is known to those skilled in the art. According to this invention xe2x80x9cmethacrylate grafted polybutadienexe2x80x9d encompasses polymers with methacrylate groups grafted to polybutadiene by any known method, for example coupling through free radical reactions, through linking groups, and so on.
Methacrylate grafted polybutadiene may be prepared for example, by any method as described in U.S. Pat. Nos. 4,857,434, 3,957,903, 4,085,166, 3,910,992 and 5,362,806, all incorporated herein by reference. Methacrylate grafted polybutadienes where the methacrylate groups are grafted onto a maleated polybutadiene as described in U.S. Pat. Nos. 4,857,434 and 5,362,806 are advantageously employed.
The preferred methacrylate grafted polybutadienes of this invention may simply be composed of maleated polybutadiene and a functional methacrylate such as hydroxyethyl methacrylate or glycidyl methacrylate, such as described in U.S. Pat. Nos. 4,857,434 and 5,362,806. They may further include other components as described in U.S. Pat. No. 5,362,806.
Some of the preferred methacrylate grafted polybutadienes of this invention are commercially available, for instance the Ricacryl(copyright) methacrylated polybutadienes available from Ricon Resins, Grand Junction, Colo. Specific examples are Ricacryl(copyright) 131MA17 and Ricacryl(copyright) 3500.
In addition to polybutadiene, other polymeric substrates may be methacrylate grafted and employed as the radiation-crosslinkable component according to this invention. Other suitable substrates for methacrylate grafting as described above are for example copolymers of ethylene, propylene and diene monomers.
Other examples of radiation crosslinkable components include glycidyl ethers of polyhydric alcohols such as those described in U.S. Pat. No. 3,910,922, incorporated herein by reference.
Modifications to the crosslinkable component are possible such as incorporation of tetrafluoroethylene monomer or styrene monomer in the backbone which may impart desirable properties other than sites for crosslinking.
The polyolefin composition also includes a photoinitiator, or free radical initiator, to facilitate curing of the polyolefin composition when irradiated. The photoinitiator may include any compounds capable of initiating free radical cleavage to crosslink the radiation-crosslinkable component. Suitable photoinitiators typically include benzoin and benzoin ether derivatives; benzil ketal derivatives; xcex1,xcex1-dialkyoxyacetophenone derivatives; xcex1-aminoalkylketone derivatives; xcex1-hydroxyalkylketone derivatives; mono- or bis-acylphosphine oxides; mono- or bis-acylphosphine sulfides; phenylglyoxylate derivatives; O-acyl-2-oximino ketone derivatives; benzophenone and its derivatives; Michler""s ketone and its derivatives; thioxanthone and its derivatives; and all the polymer-bound compounds of the type mentioned above. and the like. Specific photoinitiators can include for example 2,2-dimethoxy-2-phenylacetophenone, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide, 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)-1-butanone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-propan-1-one and 1-hydroxy-cyclohexylphenyl ketone. Preferred photoinitiators are of the type-benzil ketal derivatives and acylphosphine oxides or a mixture thereof. The photoinitiator is typically present in an amount sufficient to initiate crosslinking of the radiation-crosslinkable component when the polyolefin composition is exposed to radiation. Preferably, the photoinitiator is present in an amount of about 0.01 to 5 weight percent, more preferably about 0.05 to 4 weight percent, and most preferably about 0.1 to 3 weight percent, of the polyolefin composition. As photoinitiators tend to be costly, it is also preferred to use the least amount of photoinitiator necessary to cure the polyolefin composition in a sufficiently rapid manner.
Fillers may optionally be included within the polyolefin compositions of the present invention. Calcium carbonate, clay, talc, mica, wollastonite, glass, silica, zinc oxide, titanium dioxide, and the like are all suitable fillers for use with the polyolefins. The most appropriate fillers are typically selected depending upon the desired qualities in the final polyolefin products, and selecting such fillers is readily accomplished by one of ordinary skill in the art. The fillers are typically present in an amount of about 1 to 30 weight percent, and preferably between 5 to 15 weight percent, of the polyolefin composition.
To prepare the polyolefin composition, a polyolefin component, at least one radiation-crosslinkable component, at least one photoinitiator, and any optional filler(s) are combined to form a curable composition. The various components are typically mixed and the radiation-crosslinkable component, photoinitiator, and polyolefin component are preferably, substantially uniformly dispersed.
The polyolefin composition can also include one or more stabilizers to impart stability to the composition during mixing, during mechanical processing and during the intended end use application which may include exposure to elevated temperatures or exposure to sunlight or both. The stabilizers of the instant invention may be selected from the following:
1. Antioxidants
1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(xcex1-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1xe2x80x2-methylundec-1xe2x80x2-yl)-phenol, 2,4-dimethyl-6-(1xe2x80x2-methylheptadec-1xe2x80x2-yl)phenol, 2,4-dimethyl-6-(1xe2x80x2-methyltridec-1xe2x80x2-yl)phenol and mixtures thereof.
1.2. Alklthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octa-decyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
1.4. Tocopherols, for example xcex1-tocopherol, xcex2-tocopherol, xcex3-tocopherol, xcex4-tocopherol and mixtures thereof (Vitamin E).
1.5. Hydroxylated thiodiphenyl ethers, for example 2,2xe2x80x2-thiobis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-thiobis(4-octylphenol), 4,4xe2x80x2-thiobis(6-tert-butyl-3-methylphenol), 4,4xe2x80x2-thiobis(6-tert-butyl-2-methylphenol), 4,4xe2x80x2-thiobis-(3,6-di-sec-amylphenol), 4,4xe2x80x2-bis-(2,6-dimethyl-4-hydroxyphenyl)disulfide.
1.6. Alkylidenebisphenols, for example 2,2xe2x80x2-methylenebis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-methylenebis(6-tert-butyl-4-ethylphenol), 2,2xe2x80x2-methylenebis[4-methyl-6-(xcex1-methylcyclohexyl)phenol], 2,2xe2x80x2-methylenebis(4-methyl-6-cyclohexylphenol), 2,2xe2x80x2-methylenebis(6-nonyl-4-methylphenol), 2,2xe2x80x2-methylenebis(4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidenebis(4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2xe2x80x2-methylenebis[6-(xcex1-methylbenzyl)-4-nonylphenol], 2,2xe2x80x2-methylenebis[6-(xcex1,xcex1-dimethylbenzyl)-4-nonyl-phenol], 4,4xe2x80x2-methylenebis(2,6-di-tert-butylphenol), 4,4xe2x80x2-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methyl-phenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercapto-butane, ethylene glycol bis[3,3-bis(3xe2x80x2-tert-butyl-4xe2x80x2-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxy-phenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
1.7. O-, N- and S-benzyl compounds, for example 3,5,3xe2x80x2,5xe2x80x2-tetra-tert-butyl-4,4xe2x80x2-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.
1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of xcex2-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]octane.
1.15. Esters of xcex2-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, di-ethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)-oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
1.18. Ascorbic acid or derivatives, for example, a salt or ester of ascorbic acid, such as ascorbyl palmitate, dipalmitate L-ascorbate, sodium L-ascorbate-2-sulfate, organ ascorbic salt, such as sodium, potassium, and calcium, or mixtures thereof.
1.19. Aminic antioxidants, for example N,Nxe2x80x2-di-isopropyl-p-phenylenediamine, N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, N,Nxe2x80x2-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,Nxe2x80x2-bis-(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-methylheptyl)-p-phenylenediamine, N,Nxe2x80x2-dicyclohexyl-p-phenylenediamine, N,Nxe2x80x2-diphenyl-p-phenylenediamine, N,Nxe2x80x2-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-Nxe2x80x2-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-Nxe2x80x2-phenyl-p-phenylenediamine, N-(1-methylheptyl)-Nxe2x80x2-phenyl-p-phenylenediamine, N-cyclohexyl-Nxe2x80x2-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,Nxe2x80x2-dimethyl-N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,pxe2x80x2-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4xe2x80x2-diaminodiphenylmethane, 4,4xe2x80x2-diaminodiphenylmethane, N,N,Nxe2x80x2,Nxe2x80x2-tetramethyl-4,4xe2x80x2-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, Bis[4-(1xe2x80x2,3xe2x80x2-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazin, N,N,Nxe2x80x2,Nxe2x80x2-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
2. UV Absorbers and Light Stabilisers
2.1. 2-(2xe2x80x2-Hydroxyphenyl)benzotriazoles, for example 2-(2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)-benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(5xe2x80x2-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(2xe2x80x2-hydroxy-5xe2x80x2-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-butyl-2xe2x80x2-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-sec-butyl-5xe2x80x2-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(2xe2x80x2-hydroxy-4xe2x80x2-octyloxyphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-amyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-bis-(xcex1,xcex1-dimethylbenzyl)-2xe2x80x2-hydroxyphenyl)benzotriazole, mixture of 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-5xe2x80x2-[2-(2-ethylhexyloxy)-carbonylethyl]-2xe2x80x2-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-octyloxycarbonylethyl)phenyl)-benzotriazole, 2-(3xe2x80x2-tert-butyl-5xe2x80x2-[2-(2-ethylhexyloxy)carbonylethyl]-2xe2x80x2-hydroxyphenyl)-benzotriazole, 2-(3xe2x80x2-dodecyl-2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)benzotriazole, and 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2xe2x80x2-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3xe2x80x2-tert-butyl-5xe2x80x2-(2-methoxycarbonylethyl)-2xe2x80x2-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol300;, where R=3xe2x80x2-tert-butyl4xe2x80x2-hydroxy-5xe2x80x2-2H-benzotriazol-2-ylphenyl.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2xe2x80x2,4xe2x80x2-trihydroxy and 2xe2x80x2-hydroxy-4,4xe2x80x2-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates, for example ethyl xcex1-cyano-xcex2,xcex2-diphenylacrylate, isooctyl xcex1-cyano-xcex2,xcex2-di-phenylacrylate, methyl xcex1-carbomethoxycinnamate, methyl xcex1-cyano-xcex2-methyl-p-methoxy-cinnamate, butyl xcex1-cyano-xcex2-methyl-p-methoxy-cinnamate, methyl xcex1-carbomethoxy-p-methoxycinnamate and N-(xcex2-carbomethoxy-xcex2-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2xe2x80x2-thio-bis-[4-(1,1,3,3-tetra-methylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensate of N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, 1,1xe2x80x2-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dion, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate of N,Nxe2x80x2-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl )-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-1-(1 ,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5]decane and epichlorohydrin.
2.7. Oxamides, for example 4,4xe2x80x2-dioctyloxyoxanilide, 2,2xe2x80x2-diethoxyoxanilide, 2,2xe2x80x2-dioctyloxy-5,5xe2x80x2-di-tert-butoxanilide, 2,2xe2x80x2-didodecyloxy-5,5xe2x80x2-di-tert-butoxanilide, 2-ethoxy-2xe2x80x2-ethyloxanilide, N,Nxe2x80x2-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2xe2x80x2-ethoxanilide and its mixture with 2-ethoxy-2xe2x80x2-ethyl-5,4xe2x80x2-di-tert-butoxanilide and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxy-phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.
3. METAL DEACTIVATORS, for example N,Nxe2x80x2-diphenyloxamide, N-salicylal-Nxe2x80x2-salicyloyl hydrazine, N,Nxe2x80x2-bis(salicyloyl) hydrazine, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,Nxe2x80x2-diacetyladipoyl dihydrazide, N,Nxe2x80x2-bis(salicyloyl)oxalyl dihydrazide, N,Nxe2x80x2-bis(salicyloyl)thiopropionyl dihydrazide.
4. PHOSPHITES AND PHOSPHONITES, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4xe2x80x2-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methyl-phenyl)methylphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.
5. HYDROXYLAMINES, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
6. NITRONES, for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
7. THIOSYNERGISTS, for example, dilauryl thiodipropionate or distearyl thiodipropionate.
8. PEROXIDE SCAVENGERS, for example esters of xcex2-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(xcex2-dodecylmercapto)propionate.
9. BASIC CO-STABILISERS, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.
10. OTHER ADDITIVES, for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
11. BENZOFURANONES AND INDOLINONES, for example those disclosed in U.S. Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643, DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3xe2x80x2-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
The concentration of the costabilizer in the thermoplastic polyolefin composition is usually from 0.1 to 5 percent by weight of the composition.
The polyolefin composition is then preferably formed into a desired product by a variety of conventional means, such as injection molding, coinjection molding, blow molding, extrusion, and the like. One of ordinary skill in the art can envision a broad array of useful, desired products easily manufactured by the present invention, including electrical components such as electrode manufacture or insulation, surface treatment of a variety of materials, and automotive parts. A variety of applications may be useful just in the automotive field, although they apply to a variety of other fields of endeavor. It is clear that interior and exterior automotive applications such as instrument panels, thermoformed skins, bumper fascia, claddings, and other interior and exterior trim components can be readily produced with superior durability due to the present invention.
The polyolefin composition in its uncured state is cured by subjecting the composition to irradiation. The radiation-crosslinkable component crosslinking is initiated by a source of ionizing radiation capable of producing free radicals, such as gamma, UV, electron beam, visible, microwave, or infrared radiation. More than one type of radiation may be used, although this is typically avoided due to cost considerations. Preferably, UV or electron beam radiation is used for the curing process.
For example, when UV radiation is used as the radiation source, the curing process requires at least one UV lamp that directs UV light onto the formulated product. These UV lamps may provide either arc light, which includes a medium pressure mercury lamp and a high pressure xenon lamp, or laser light. The photoinitiator(s) used must have an absorption spectra that at least partially overlaps with the emission spectra of the UV lamp, such that the photoinitiator is capable of absorbing the UV energy. The photoinitiator rapidly initiates a chemical reaction that quickly converts the resin, or radiation-crosslinkable component, into a cured (crosslinked) form. This photoinitiated curing typically occurs in less than one second, although this will depend on the rate of UV energy transfer. The UV energy preferably has a wavelength of between about 300 to 400 nm. The radiation source typically provides energy at a rate of about 2-15 J/cm2. For example, a lamp of about 1-6 J/cm2 would typically take less than one second to cure a thermoplastic polyolefin composition. It of course is possible for other cure mechanisms (such as thermal or moisture induced curing) to continue well after photoinitiated crosslinking is complete.
A test was developed by Solvay Engineered Polymers to measure relative surface scratch resistance. For this test, the test specimens are at least 4xe2x80x3xc3x974xe2x80x3 (100 mmxc3x97100 mm) in dimensions, with a hole drilled in the middle for mounting. A Taber Abrasion test machine (described further in ASTM D1044) was modified by substituting a stainless steel slider with a sharp tip (radius ca. 0.25 mm) in place of the sanding wheels to scratch the surface of the specimens. With the tip offset 34 mm from the center of rotation and the turntable spinning at 72 rpm, the actual sliding velocity is equal to 25 mm/sec, which is similar to the condition of someone scratching a surface at normal speed with a fingernail. The test is terminated after one single revolution. The normal load used for this test is 1 lb. Upon completion of the test, the specimens are then rated visually on a numerical scale of 1 to 5 (1=excellent, hardly any marring is visible; 5=badly scratched). The width of the wear track and the characteristics of the failure surface can also be further studied with an optical microscope or more sophisticated instruments such as surface profilometer and scanning force microscope. The typical dimensions of the wear paths corresponding to the mar ratings are as follows:
A value of 1.5 or less in this test is indicative of very good or excellent performance.

Polyolefin materials having enhanced surface durability and methods of making the same by exposure to radiation


An exercise device is disclosed for facilitating blood circulation in the lower extremities of a person's legs and feet. The exercise device includes a one piece member having upper surface and a lower surface. The lower surface has an arcuate section designed to directly contact a floor. The arcuate section is located between first and second planar sections. Each of the first and second planar sections is inclined downward at an angle relative to the arcuate section. A pair of spaced apart ramps is formed in the upper surface and each extends downwardly from a back surface to a front surface. Each of the ramps is designed to receive a portion of a person's foot while an adjoining heel of each foot rest on the floor. The person can rock the exercise device back and forth by shifting his weight from one foot to the other.

Today, many people sit for extended periods of time at a work station, as a passenger in an airplane or in a car, on a bus, on a train, etc. In the new computer age, many adults and children spend an enormous amount of time sitting in front of a desktop or a laptop computer taking care of business, surfing the web, playing video games, purchasing merchandise, etc. It is well known that prolonged sitting, such as at a desk, in front of a computer screen, seated at an airport terminal, or as a passenger in an airplane, car, bus or train results in poor blood circulation in the lower extremities, especially in the lower portion of the legs below the knees and in the feet. A known remedy for such poor circulation is to periodically exercise the lower extremities. Where the person has the option of periodically getting up and walking about, such walking can alleviate at least some of the poor circulation issues. However, many people work at jobs which require that they remain at their work stations for prolonged periods of time, negating the option of getting up and walking around to address such blood circulation issues.
For those who are unable to get up and walk around, it is desirable that they engage in some form of exercise while sitting.
Today, a variety of exercise devices exist which are primarily designed to be used in a large open area such as a gym. Many are large and are formed from metal, metal alloys, steel, stainless steel, cast iron, etc. so as to be sturdy and long lasting. Some of these exercise devices are designed to be stepped onto or to be stood on while performing a particular exercise. Such exercise devices are normally not moved from one location to another but are positioned such that the person who is working out rotates among the various pieces of exercise equipment. Each exercise device may be designed to work only certain muscles of a person's body. Very few exercise devices are manufactured as a one piece, lightweight portable device that can be easily carried by a person to and from work or by a person who is traveling as a passenger on an airplane, car, bus or train. Many exercise devices are not sized to be positioned under a desk or computer table, either in a home environment, at work or on public transportation.
A related problem of poor blood circulation in a person's legs or feet exists among people who have limited mobility for other reasons. Such reasons include but are not limited to: those who have a leg, ankle or foot injury, those with leg neuropathy or leg degradations, those who are too weak to walk, the aged, those afflicted with a disease or those recovering from certain medical procedures, such as a foot operation, and the like. In addition, some medically challenged people, such as the handicapped or wheelchair bound individuals, as well as those suffering from a temporary or a permanent infirmity may not be able to stand on their own. All of the above individuals would benefit from a one piece, lightweight exercise device that they could use to properly exercise their legs and/or feet to ensure proper levels of blood circulation.
Now, an exercise device for facilitating blood circulation in the lower extremities of a person's legs and feet has been invented. The one piece, lightweight exercise device is relatively small and portable, and is easily carried and moved. The exercise device can be placed on the floor under a person's desk, work station or computer table or it can be placed on the floor in front of a person seated in a chair or seat. The chair or seat can be at home, in a work environment, in an airport terminal, on an airplane, a car, a bus, a train, etc.

One-piece, lightweight extremity exercise device


A method and composition for treating a patient suffering from a disease, disorder or condition and associated pain include the administration to the patient of a therapeutically effective amount of a neurotoxin selected from a group consisting of Botulinum toxin types A, B, C, D, E, F and G.

The present invention provides novel methods for treating various disorders and conditions, with Botulinum toxins. Importantly, the present invention provides methods useful in relieving pain related to muscle activity or contracture and therefore is of advantage in the treatment of, for example, muscle spasm such as Temporomandibular Joint Disease, low back pain, myofascial pain, pain related to spasticity and dystonia, as well as sports injuries, and pain related to contractures in arthritis.
Heretofore, Botulinum toxins, in particular Botulinum toxin type A, has been used in the treatment of a number of neuromuscular disorders and conditions involving muscular spasm; for example, strabismus, blepharospasm, spasmodic torticollis (cervical dystonia), oromandibular dystonia and spasmodic dysphonia (laryngeal dystbnia). The toxin binds rapidly and strongly to presynaptic cholinergic nerve terminals and inhibits the exocytosis of acetylcholine by decreasing the frequency of acetylcholine release. This results in local paralysis and hence relaxation of the muscle afflicted by spasm.
For one example of treating neuromuscular disorders, see U.S. Pat. No. 5,053,005 to Borodic, which suggests treating curvature of the juvenile spine, i.e., scoliosis, with an acetylcholine release inhibitor, preferably Botulinum toxin A.
For the treatment of strabismus with Botulinum toxin type A, see Elston, J. S., et al., British Journal of Ophthalmology, 1985, 69, 718-724 and 891-896. For the treatment of blepharospasm with Botulinum toxin type A, see Adenis, J. P., et al., J. Fr. Ophthalmol., 1990, 13 (5) at pages 259-264. For treating squint, see Elston, J. S., Eye, 1990, 4(4):VII. For treating spasmodic and oromandibular dystonia torticollis, see Jankovic et al., Neurology, 1987, 37, 616-623.
Spasmodic dysphonia has been treated with Botulinum toxin type A. See Blitzer et al., Ann. Otol. Rhino. Laryngol, 1985, 94, 591-594. Lingual dystonia was treated with Botulinum toxin type A according to Brin et al., Adv. Neurol. (1987) 50, 599-608. Finally, Cohen et al., Neurology (1987) 37 (Suppl. 1), 123-4, discloses the treatment of writer""s cramp with Botulinum toxin type A.
The term Botulinum toxin is a generic term embracing the family of toxins produced by the anaerobic bacterium Clostridium botulinum and, to date, seven immunologically distinct neurotoxins have been identified. These have been given the designations A, B, C, D, E, F and G. For further information concerning the properties of the various Botulinum toxins, reference is made to the article by Jankovic and Brin, The New England Journal of Medicine, No. 17, 1990, pp. 1186-1194, and to the review by Charles L. Hatheway in Chapter 1 of the book entitled Botulinum Neurotoxin and Tetanus Toxin, L. L. Simpson, Ed., published by Academic Press Inc. of San Diego, Calif., 1989, the disclosures in which are incorporated herein by reference.
The neurotoxic component of Botulinum toxin has a molecular weight of about 150 kilodaltons and is thought to comprise a short polypeptide chain of about 50 kD which is considered to be responsible for the toxic properties of the toxin, i.e., by interfering with the exocytosis of acetylcholine, by decreasing the frequency of acetylcholine release, and a larger polypeptide chain of about 100 kD which is believed to be necessary to enable the toxin to bind to the pre-synaptic membrane.
The xe2x80x9cshortxe2x80x9d and xe2x80x9clongxe2x80x9d chains are linked together by means of a simple disulfide bridge. (It is noted that certain serotypes of Botulinum toxin, e.g., type E, may exist in the form of a single chain un-nicked protein, as opposed to a dichain. The single chain form is less active but may be converted to the corresponding dichain by nicking with a protease, e.g., trypsin. Both the single and the dichain are useful in the method of the present invention.)
In general, four physiologic groups of C. botulinum are recognized (I, II, III, IV). The organisms capable of producing a serologically distinct toxin may come from more than one physiological group. For example, Type B and F toxins can be produced by strains from Group I or II. In addition, other strains of clostridial species (C. baratii, type F; C. butyricum, type E; C. novyi, type C1 or D) have been identified which can produce botulinum neurotoxins.
Immunotoxin conjugates of ricin and antibodies, which are characterized as having enhanced cytotoxicity through improving cell surface affinity, are disclosed in European Patent Specification 0 129 434. The inventors note that botulinum toxin may be utilized in place of ricin.
Botulinum toxin is obtained commercially by establishing and growing cultures of C. botulinum in a fermenter and then harvesting and purifying the fermented mixture in accordance with known techniques.
Botulinum toxin type A, the toxin type generally utilized in treating neuromuscular conditions, is currently available commercially from several sources; for example, from Porton Products Ltd. UK, under the trade name xe2x80x9cDYSPORT,xe2x80x9d and from Allergan, Inc., Irvine, Calif., under the trade name BOTOX(copyright).
It is one object of the invention to provide novel treatments of neuromuscular disorders and conditions with various Botulinum toxin types. It is another object of the present invention to relieve pain with various Botulinum toxin types.
The present invention provides a method for relieving pain, associated with muscle contractions, a composition and a method of treating conditions such as cholinergic controlled secretions including excessive sweating, lacrimation and mucus secretions and a method for treating smooth muscle disorders including, but not limited to, spasms in the sphincter of the cardiovascular arteriole, gastrointestinal system, urinary, gall bladder and rectum, which method comprises administering to the patient suffering from said disorder or condition a therapeutically effective amount of Botulinum toxin selected from the group consisting of Botulinum toxin types B, C, D, E, F and G.
Each serotype of Botulinum toxin has been identified as immunologically different proteins through the use of specific antibodies. For example, if the antibody (antitoxin) recognizes, that is, neutralizes the biological activity of, for example, type A it will not recognize types B, C, D, E, F or G.
While all of the Botulinum toxins appear to be zinc endopeptidases, the mechanism of action of different serotypes, for example, A and E within the neuron appear to be different than that of Type B. In addition, the neuronal surface xe2x80x9creceptorxe2x80x9d for the toxin appears to be different for the serotypes.
In the area of use of the Botulinum toxins in accordance with the present invention with regard to organ systems which involve the release of neurotransmitter, it is expected to introduce the toxins A, B, C, D, E, F, and G directly by local injections.
The Botulinum toxins used according to the present invention are Botulinum toxins type A, B, C, D, E, F and G.
The physiologic groups of Clostridium botulinum types are listed in Table I.
These toxin types may be produced by selection from the appropriate physiologic group of Clostridium botulinum organisms the organisms designated as Group I are usually referred to as proteolytic and produce Botulinum toxins of types A, B and F. The organisms designated as Group II are saccharolytic and produce Botulinum toxins of types B, E and F. The organisms designated as Group III produce only Botulinum toxin types C and D and are distinguished from organisms of Groups I and II by the production of significant amounts of propionic acid. Group IV organisms only produce neurotoxin of type G. The production of any and all of the Botulinum toxin types A, B, C, D, E, F and G are described in Chapter 1 of Botulinum Neurotoxin and Tetanus Toxin, cited above, and/or the references cited therein. Botulinum toxins types B, C, D, E, F and G are also available from various species of clostridia.
Currently fourteen species of clostridia are considered pathogenic. Most of the pathogenic strains produce toxins which are responsible for the various pathological signs and symptoms. Organisms which produce Botulinum toxins have been isolated from botulism outbreaks in humans (types A, B, E and F) and animals (types C and D). Their identities were described through the use of specific antitoxins (antibodies) developed against the earlier toxins. Type G toxin was found in soil and has low toxigenicity. However, it has been isolated from autopsy specimens, but thus far there has not been adequate evidence that type G botulism has occurred in humans.
Preferably, the toxin is administered by means of intramuscular injection directly into a local area such as a spastic muscle, preferably in the region of the neuromuscular junction, although alternative types of administration (e.g., subcutaneous injection), which can deliver the toxin directly to the affected region, may be employed where appropriate. The toxin can be presented as a sterile pyrogen-free aqueous solution or dispersion and as a sterile powder for reconstitution into a sterile solution or dispersion.
Where desired, tonicity adjusting agents such as sodium chloride, glycerol and various sugars can be added. Stabilizers such as human serum albumin may also be included. The formulation may be preserved by means of a suitable pharmaceutically acceptable preservative such as a paraben, although preferably it is unpreserved.
It is preferred that the toxin is formulated in unit dosage form; for example, it can be provided as a sterile solution in a vial or as a vial or sachet containing a lyophilized powder for reconstituting a suitable vehicle such as saline for injection.
In one embodiment, the Botulinum toxin is formulated in a solution containing saline and pasteurized human serum albumin, which stabilizes the toxin and minimizes loss through non-specific adsorption. The solution is sterile filtered (0.2 micron filter), filled into individual vials and then vacuum-dried to give a sterile lyophilized powder. In use, the powder can be reconstituted by the addition of sterile unpreserved normal saline (sodium chloride 0.9% for injection).
The dose of toxin administered to the patient will depend upon the severity of the condition; e.g., the number of muscle groups requiring treatment, the age and size of the patient and the potency of the toxin. The potency of the toxin is expressed as a multiple of the LD50 value for the mouse, one unit (U) of toxin being defined as being the equivalent to that amount, on a per mouse basis, that kills 50% of a group of Swiss-Webster mice weighing between 17 and 22 grams each.
The dosages used in human therapeutic applications are roughly proportional to the mass of muscle being injected. Typically, the dose administered to the patient may be up from about 0.01 to about 1,000 units; for example, up to about 500 units, and preferably in the range from about 80 to about 460 units per patient per treatment, although smaller of larger doses may be administered in appropriate circumstances such as up to about 50 units for the relief of pain and in controlling cholinergic secretions.
As the physicians become more familiar with the use of this product, the dose may be changed. In the Botulinum toxin type A, available from Porton, DYSPORT, 1 nanogram (ng) contains 40 units. 1 ng of the Botulinum toxin type A, available from Allergan, Inc., i.e., BOTOX(copyright), contains 4 units. The potency of Botulinum toxin and its long duration of action mean that doses will tend to be administered on an infrequent basis. Ultimately, however, both the quantity of toxin administered and the frequency of its administration will be at the discretion of the physician responsible for the treatment and will be commensurate with questions of safety and the effects produced by the toxin.
In some circumstances, particularly in the relief of pain associated with sports injuries, such as, for example, charleyhorse, botulinum type F, having a short duration activity, is preferred.

Method for treating a cholinergic influenced sweat gland